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Supporting Information

The Marvin Sktech Software was used to evaluate Alliins protonation state at physiological pH (7.2).
The result of the simulation is shown in Fig. S6. The Infrared and Raman spectra presented in the paper are
for the most stable conformer, depicted in Fig. 1b and labeled here Alliin 1. In Fig.S7, we present the DFT
calculated vibrational spectra of both conformers together with the Allicin theoretical spectra. We also provide
the structural parameters of both Alliins conformers in Table S3, and complete vibrational assignments of
Alliins normal modes (not discussed in the paper) in Table S4.

Figure SF1. Marvin sketch computation of Alliins Microspecies distribution along 0 14 pH range.

Figure SF2. DFT-calculated Infrared (left) and Raman (right) spectra of both Alliin conformers and Allicin in
the wanumber range 1100-1800 cm-1.

Figure SF3. DFT-calculated Infrared (left) and Raman (right) spectra of Alliin in the 1800-3600 cm -1 range.
The infrared experimental spectrum of Alliin in the 1800-3900 cm -1 wavenumber range is shown at the top-left
of Fig. SF3. It shows a series of strongly shifted bands with large broadening, probably due to the lack of
homogeneity of the Alliin powder samples. Water effects (OH stretching) can contribute to the shape of the
experimental curve near 3600 cm -1. Experimental peaks at 2030, 2580, and 3080 cm -1 are assigned to the
theoretical normal modes M50, M59, and M60 (Fig. SF3, bottom-left). The Raman experimental spectrum, on
the other hand, exhibits much less broadening between 2700 and 3150 cm -1 (top-right), while the theoretical
curve is shifted up by about 200 cm-1. The main Raman peaks are assigned to the normal modes M55, M56,
M57, and M58.

Table ST1. Calculated structural parameters for the lowest energy Alliin conformers. Bond lengths and
angles are displayed in and degrees, respectively.
Atoms
C1H3
C1H2
C1C4
C4H5
C4C6
C6H7
C6H8
C6S15
S15O16
S15C9
C9H10
C9H11
C9C12
C12H13
C12C14
C12N17
N17H18
N17H19
N17H20
C14O21
C14O22

Bond lenght
Conformer 1

Conformer 2

1.0853
1.0833
1.3285
1.0862
1.4951
1.0911
1.0917
1.8308
1.5415
1.8261
1.0901
1.0910
1.5226
1.0913
1.5627
1.4979
1.0189
1.0322
1.0462
1.2377
1.2489

1.0851
1.0833
1.3284
1.0861
1.4940
1.0917
1.0927
1.8294
1.5367
1.8234
1.0937
1.0902
1.5226
1.0893
1.5652
1.4975
1.0204
1.0298
1.0380
1.2378
1.2469

Atoms
H2C1H3
H2C1C4
C1C4H5
H5C4C6
C4C6H8
H8C6S15
C6S15C9
O16S15C9
H11C9C12
C9C12H13
C13C12N17
N17C12C14
O22C14O21

Bond angle
Conformer 1

Conformer 2

117.48
121.24
120.45
116.64
112.88
106.16
101.57
104.54
111.30
107.36
107.48
108.31
129.96

117.48
121.19
120.47
116.61
112.30
105.63
97.34
103.42
108.91
111.21
108.40
108.15
103.31

Table ST2. Alliin infrared and Raman active normal modes in the wavenumber range 400-1800 cm -1. The assignments of Xiao et al. 18
are also shown. is given in cm-1 and the deviations cm-1 (%) of each theoretical normal mode with respect to experimental values
are provided as well.
Mode

Infrared

THE

Raman

A/P (%) Our

Our

Xiao

Our

Xiao

A/P (%) Wang

324

Skel

M13

378

421

417

415

C9H10H11(38), N17H18H19H20(15)

Skel

M14

442

463

461

461

C1C4C6(74)

NH3

M15

524

522

503

500

C12C9N17(60), C9H10H11(10)

Skel

M16

540

544

543

544

Skel

Skel

M17

580

585

588

588

S15C6(42), C1C4C6(26)

COO-

M18

610

614

617w

619

620m

Skel

COO-

M19

678

702

691w

693

693vs

S15C9(63)

C-S

M20

758

746

744w

745

745vs

S15C6(25), C1H2H3(24)

COO-

M21

803

787

783m

790

790vs

C14O21O22(37)

CH2, COO-

M22

849

841

850w

840

837m

C14O21O22(40), C9H10H11(13)

CH2

M23

888

873

873

C1H2H3(68), C6H7H8(13), C9H10H11(10)

M24

901

931

919s

931

934m

C9C12C14N17(33)

CH2

964m

967m

C-C

M25

956

990

989m

972

992w

S15O16(33), C1H2H3(11), C9H10H11(10)

C-C, C-N

M26

962

1019

S15O16(63), C1H2H3(20)

M27

978

1040

Skel

M28

989

990

C1H2H3(96)

M29

1034

1055

1048w

1054

1051w

C1H2H3(92)

S=O, C-N

M30

1087

1085

1100

C9C12C14(52)

M31

1106

1119

1124

M32

1145

1146

1131m

1148

M33

1147

1157

1158

M34

1231

1195

1229w

1197

M35

1246

1215

1207

M36

1278

1272

1277

M37

1314

1294

1301s

1291

M38

1325

---

1297

M39

1346

1319

1317

M40

1385

1357

1342s

1361

M41

1412

1391

1405

M42

1427

1430

M43

1442

1398

1418vs

M44

1460

1453

M45

1494

1431

M46

1614

1519

1496vs

M47

1669

1593

1582s

1593

M48

1723

1638

1617s

C1H2H3(40), C6H7H8(41)

1138s
N17H18H19H20(69)

NH3+

C9C12(14), N17H18H19H20(48)

C9C12(14), C9H10H11(15)

C7H7H8

C7H7H8(15), C9H10H11(10), C1C4H2H5(67)

C6H7H8(76), C1H2H3(10), C9H10H11(10)

C9H10H11(37), N17H18H19H20(20)

CH2, CH

C1C4H3H5(88), C6H7H8(10)

C9H10H11(49)

N17H18H19H20(43)

CH2, CH

SC14O21O22(70), C9H10H11(10)

C1H2H3(89), C9H10H11(10)

C9H10H11(84)

COO-

C1H2H3(89), C9H10H11(10)

SN17H18H19H20(77)

1197s

1290vs

1336m

1404vs

1502w
AN17H18H19H20(87)

AN17H18H19H20(98)
1636vs
AC14O21O22(82), C1C4(16)

NH3+

NH3+

NH3+

M49

1725

1646

1643

C1C4(70), AC14O21O22(10)

The symbols: ,,,,,and stand for stretching, in-plane angular deformation, out-of-plane deformation, twisting, rocking,
wagging and bending modes in this respective order, subscripts A and S stand for symmetric and asymmetric respectively and the term
Skel is assign to a vibration mode which the PED is distributed throughout the whole molecular skeleton.

Table ST3. All calculated normal modes for the Alliin molecule. The wavenumber is given in cm-1, with respective Infrared and/or Raman
experimental counterparts vibrational assignments. The deviation of each theoretical normal mode in comparison with experiment (in cm-1), is
presented as well .
Mode

THE

M01
M02
M03
M04
M05
M06
M07
M08
M09
M10
M11
M12
M13
M14
M15
M16
M17
M18
M19
M20
M21
M22
M23
M24
M25
M26
M27
M28
M29
M30
M31
M32
M33
M34
M35
M36
M37
M38
M39
M40
M41
M42
M43
M44
M45
M46
M47
M48
M49
M50
M51
M52
M53
M54
M55
M56
M57
M58
M59
M60

50
66
80
89
120
161
252
262
303
321
340
359
378
441
523
540
580
610
678
757
802
849
888
900
956
962
978
989
1033
1087
1106
1145
1147
1231
1246
1278
1314
1325
1346
1385
1412
1427
1442
1460
1494
1614
1669
1723
1725
3013
3089
3105
3120
3160
3164
3169
3187
3258
3333
3549

Experimental
IR

Raman

416
460
503
542
588
619
693
744
790
840
873
930
972

989
1054
1100
1124
1147
1157
1196
1207
1277
1291
1297
1316
1361
1404
1429

1453

1593
--1643

421
462
521
544
584
613
701
746
786
841
872
930
989
1018
1039

1054
1084
1118
1146
1156
1194
1214
1272
1294

1318
1357
1390

1397

1430
1519
1592
1637
1645

IR (%)

Raman (%)

-43 (10.2)
-21 (4.5)
+2 (0.3)
-4 (0.7)
-4 (0.7)
-3 (0.4)
-23 (3.2)
+11 (1.4)
+16 (2.0)
+8 (0.9)
+16 (1.8)
-30 (3.2)
-33 (3.3)
-56 (5.5)
-61 (5.8)

-21 (1.9)
+3 (0.2)
-12 (1.0)
-1 (0)
-9 (0.7)
+37 (3.0)
32 (2.6)
+6 (0.4)
+20 (1.5)

+28 (2.1)
+28 (2.0)
+2 (1.5)

+45 (3.2)

+64 (4.4)
+95 (6.2)
+77 (4.8)
+86 (5.2)
+70 (4.8)

-38 (9.1)
-19 (4.1)
+20 (3.9)
-2 (0.3)
-8 (1.3)
-9 (1.4)
-15 (2.1)
+13 (1.7)
+12 (1.5)
+9 (1.0)
+15 (1.7)
-30 (3.2)
-16 (1.6)

-21 (1.9)
-13 (1.1)
-18 (1.6)
-2 (1.0)
-10 (0.8)
+35 (2.9)
+39 (3.2)
+1 (0)
+23 (1.7)
+28 (2.1)
+30 (2.2)
+24 (1.7)
+8 (0.5)
-2 (0.1)

+7 (0.4)

+76 (4.7)
--+82 (4.9)

Mode Assignement PED (%)


Skel
C1C4C6S15(70)
H5C4C6S15(72)
C4C6S15O16(76)
N17C12C14(58)
S15C6C9(58)
C12C14N17(21), C9C12N17(29)
C4C6S15(60)
C12C14N17(22)
C4C6S15(42)
C12C14N17(10), C6C9S15(45)
Skel
C9H10H11(38), N17H18H19H20(15)
C1C4C6(74)
C9H10H11(10), C12C9N17(60)
Skel
S15C6(42), C1C4C6(26)
Skel
S15C9(63)
S15C6(25), C1H2H3(24)
C14O21O22(37)
C14O21O22(40), C9H10H11(13)
C1H2H3(68), C6H7H8(13), C9H10H11(10)
C9C12C14N17(33)
S15O16(33), C1H2H3(11), C9H10H11(10)
S15O16(63), C1H2H3(20)
Skel
C1H2H3(96)
C1H2H3(92)
C9C12C14(52)
C1H2H3(40), C6H7H8(41)
N17H18H19H20(69)
C9C12(14), N17H18H19H20(48)
C9C12(14), C9H10H11(15)
C7H7H8(15), C9H10H11(10), C1C4H2H5(67)
C6H7H8(76), C1H2H3(10), C9H10H11(10)
C9H10H11(37), N17H18H19H20(20)
C1C4H3H5(88), C6H7H8(10)
C9H10H11(49)
N17H18H19H20(43)
SC14O21O22(70), C9H10H11(10)
C1H2H3(89), C9H10H11(10)
C9H10H11(84)
C1H2H3(89), C9H10H11(10)
SN17H18H19H20(77)
AN17H18H19H20(87)
AN17H18H19H20(98)
C1C4(16), AC14O21O22(82)
C1C4(70), AC14O21O22(10)
N17H20(97)
SC6H7H8(99)
SC9H10H11(91)
C12H13
AC6H7H8(85)
SC1H2H3(91)
AC9H10H11(93)
C4H5(89)
AC1H2H3(97)
N17H19(97)
AN17H18H19(98)

The symbols: ,,,,,and stand for stretching, in-plane angular deformation, out-of-plane deformation, twisting, rocking, wagging and
bending modes in this respective order, subscripts A and S stand for symmetric and asymmetric respectively and the term Skel is assign to a

vibration mode which the PED is distributed throughout the whole molecular skeleton.

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